Composition of matter



Patented Dec. 24, 1940 UNITED STATES PATENT OFFICE COMPOSITION OFMATTER.

ware

No Drawing. Original application May 9, 1938, Serial No. 206,905, nowPatent No. 2,176,703

dated October 17, 1939.

Divided and this application July 14, 1939, Serial No. 284,525

7 Claims.

This invention relates to a new material or composition of matter thatis particularly adapted for use in the treatment of emulsions of mineraloil and water, such as petroleum emulsions, for the purpose ofseparating the oil from the water, our present application being adivision of our application Serial No. 206,905, filed May 9, 1938, whichhas matured as U. S. Patent No. 2,176,703, dated October 17, 1939. Inaddition to being particularly adapted for use as a demulsifizr, in theresolution of crude oil emulsions, said new material or composition ofmatter may have uses in other arts that we have not investigated.

The new material or composition of matter which constitutes thesubject-matter of our present application consists of a complex esterderived by reaction between (a) a certain kind of complex amine derivedfrom blown oils and tertiary hydroxyamines; and (b) polybasic carboxyacids. Said new compound orcomposition of matter is particularly adaptedfor use as a demulsifier for crude oil emulsions, either alone or inadmixture with conventional demulsifying agents of a compatible type.

In using said material to break petroleum emulsions of the water-in-oiltype, the emulsion is subjected to the action of a demulsifying agentconsisting of said material, thereby causing the emulsion to break downand separate into its component parts of oil and water or brine when theemulsion is permitted to remain in a quiescent state, after treatment,or is subjected to other equivalent separatory procedure.

As previously indicated, our new material or composition of matter isderived by reaction between a polybasic carboxy acid or its functionalequivalent, such as an anhydride, and a complex amine of the kindderived by reaction between a tertiary hydroxy amine and a blown oil.Polybasic carboxy acids include phthalic acid, maleic acid, malic acid,succinic acid, adipic acid, etc. Insofar that the complex amine derivedfrom a tertiary hydroxy amine and a blown oil is not a Well knownarticle of commerce, we will hereinafter describe the same in detail. Inthis connection, attention is called to our application Serial No.206,900, filed May 9, 1938, which has matured as U. S. Patent No.2,167,346, dated July 25, 1939 which is concerned with breakingpetroleum emulsions, by means of such complex amines, and also to ourco-pending applications Serial No. 180,992 and Serial No. 180,993, bothfiled December 21, 1937.

Attention is directed 'to the fact that in describing the manufacture ofthe new composition of matter which constitutes our present invention,an esterification process may appear at three different stages:

In the first place, if one had a blown fatty acid instead of a blownoil, such acidic material could be esterified in a conventional mannerwith any alcohol, i. e., ethyl alcohol, ethylene glycol, or glycerol, bymeans of intimate mixture in presence of dried HCl, at a temperatureabove Secondly, the neutral blown oil-neutral in the sense that it is inester form-is treated with a product such as triethanolamine. In thisinstance, rearrangement takes place so that an alcohol radical orradicals of the triethanolamine become combined with the oxy-acylradicals of the acidic materials present in the blown oil. Thus, thisparticular rearrangement is also an esterification.

Finally, when the complex amine is prepared, it is then subjected toesterification with a polybasic carboxy acid, such as phthalic acid. Forthe sake of convenience only, the final step of esterification involvingphthalic acid or the like will be referred to at all times as polybasiccarboxy esterification. It is understood that this designation is purelyan arbitrary procedure, in order to simplify the discussion hereinincluded which is concerned with the manufacture of these newcompositions of matter.

The subject-matter immediately following,

which is concerned with the preparation of the complex amine, is takensubstantially verbatim from our application Serial No. 206,900, filedMay 9, 1938, which has matured as U. S. Patent No. 2.167346, dated July25, 1939.

The complex amines which are subsequentlysubjected to polybasic carboxyesterification are derived from blown oils. It has long beenknown thatvarious animal, vegetable, and marine oils can be blown or oxidized soas to yield materials which differ in chemical and physical propertiesand characteristics from the parent materials from which they werederived. The oxidation process is generally conducted by means of moistor dry air, ozone, ozonized air, or a mixture of the same. It may beconducted at atmospheric pressure, or may be conducted under increasedprmsures of several atmospheres or more. Oxidation may be conducted atrelatively low temperatures, for instance, 100 C. or 130 0., or may beconducted at a much higher temperature. Oxidation may be conducted inabsence of catalysts, or in presence of catalysts. Such catalysts mayconsist of metallic salts, such as cobalt or manganese oleate, or mayconsist of organic material, such as alpha pinene or the like. Oxidationmay be conducted in a relatively short time, such as hours, or mayrequire 200 hours or more. I

The blown or oxidized oils are generally selected from unsaturated oilsof the non-drying type.

or the semi-drying type, including the marine They are may be producedfrom a mixture of oils con- .taining some proportion of such activedrying oils. In actual practice, blown oils of the kind employed invarious industries, such as the demulsiilcation of petroleum emulsions,are derived from castor oil, rapeseed oil, cottonseed oil, peanut oil,corn oil, olive oil, and various marine oils, such as sardine, herring,sperm, menhaden, and pilchard oil.

When an unsaturated fatty acid or oil, for instance, olive oil, is blownor oxidized with air, hydroxyl groups are formed at the ethylenelinkage. This is particularly true if oxidation is carried out withmoist air. It is believed that oxygen is first absorbed so as tosaturate the ethylene linkage, and that further reaction takes placewith water to produce two hydroxyl groups.

Whether or not this is the correct explanation,

it is known that hydronl groups are formed. For instance, Chemistry ofthe Oil Industry," by Southcombe, 1926, p ge 181, in speaking of blown(oxidized) oils, states as follows: Hydroxyl groups are unquestionablyformed, as the considerable rise in acetyl value proves. Patents whichdescribe conventional blown oils or conventional methods of makingvarious blown oils for various purposes (including in some instances,for the purpose of demulsifying crude oils), include the following: I

U. 8. Patent No. 1,929,399, dated October 3,

' 1933, to Fuchs; U. S. Patent No. 1,969,387, dated August '1, 1934, toTumbler; U. S. Patent No. 2,023,979. dated December 10, 1935, to Stehr;

U. S. Patent No. 2,041,729, dated May 26, 1936, to

Seymour; and U.-S. Patent No. 1,984,633; dated December 18, 1934, to DeGroote and Keiser.

Insofar that a very suitable form of a complex amine, from thestandpoint of subsequent esterincation, is derived from blown castor oilas a primary raw material, an effort will be made to describe thisproduct in considerable detail. Mild oxidation of castor oil (see"Chemical Technology and Analysis of Oils, Fats and Waxes." byLewkowitscb, 6th edition, vol. 2, p. 406) produces relatively smallmodifications in certain important chemical indices, such as the iodinevalue, the acetyl value, and the saponiflcation value.

If drastic oxidation takes place, either by continued mild oxidationfrom the very beginning of the reaction, as induced by either a highertemperature of reaction, or the presence of a catalyst, such as alphapinene, manganese ricinoleate, etc., then one obtains an oxidized oilhaving characteristics which clearly indicate that drastic oxidation hastaken place. These indices of drastic oxidation are a relatively lowiodine value, such as 65 or less, and may be as low as 40 orthereabouts; an acetyl value of approximately 160 to 200; an increasedviscosity; a specific gravity of almost 1, or even a trifle over 1 attimes; and in absence of other coloring matter, a deep orange color.

Drastically oxidized castor oil can be prepared by well known methods,or such products can be purchased on, the open market under varioustrade names, such as blown castor oil, bodied castor oil," blendedcastor oil," blended bodied castor oil," processed castor oil, oxidizedcastor oil," heavy castor oil, viscous castor oil, etc. These variousnames appear to be applied to drastically oxidized castor oils which aredifferent in degree but not diiferent in kind.

Not only may blown oils be derived by direct oxidation of the variousfats and oils, but also by direct oxidation of the fatty acids. Blownricinoleic acid maybe derived in the manner indicated in U. S. PatentNo. 2,034,941, dated March 24,1936, to De Groote, Keiser and Wirtel. It

should be noted that blown oils in the broad generic sense hereinemployed include not only the products derived by oxidation, but alsothe products derived by polymerization. Reference is made to polymerizedricinoleic acid described in U. S. Patent No. 1,901,163, dated March 1,1933, to Hinrichs. Reference is also made to polymerized castor oil orsimilar oils of the kind disclosed in application Serial No. 59,090,filed January 13, 1936, by Ivor M. Colbeth, which matured as U. S.Patent No. 2,114,651, dated April 19, 1938. It might also be desirableto point out that the expression blown oil, as herein used, contemplatesblown unsaturated liquid waxes, such as blown sperm oil. It isunderstood that in the appended claims the expressions blown oil orblown oil fatty acids" are used in this broad sense to include all thevarious materials such as esterifled blown fatty acids.

In-such instances where blown or polymerized acids are used, it willbecome apparent that these materials must be converted into an esterbefore reaction with an amine, as subsequently described. For instance,blown castor oil fatty acids, or polymerized 'ricinolelc acid can beconverted into the ethyl ester, methyl ester, propyl ester, cyclohexylester, ethylene glycol ester, glyceryl ester, or any suitable ester bymeans of conventional esterification processes. We desire specificallyto point out that the estolides of blown oils,'as described in U. S.Patent No. 2,079,762, dated May 11, 1937, to De Groote and Keiser, arenot suitable to be employed in place of blown oils, even afterconversion into a completely esterifled material by means of a selectedalcohol by conventional processes. We have found that when a blown oilis converted into an estolide, such product no longer containsthetypical blown oil acidic material. Such-estolides are not adaptable asraw materials for the manufacture of the complex amine employed in thefinal polybasic carboxy esteriflcation.

In preparing the intermediate raw material intended for esterificationin the present invention, we prefer to produce an amine by reaction witha drastically oxidized castor oil having approximately the followingcharacteristics:

Acid number 13.2to 25.0 Saponiflcation number 230.5 to 274.0 Iodinenumber 43.5to 55.0 Acetyl number 164.0 to 192.0 Hydroxyl value 188.0 to220.0 Percent unsaponiiiable matter 1.1 Percent nitrogen 0.0 Percent SO;0.0 Percent ash Trace Our usual procedure is to eliminate carboxylicacidity of a blown oil by means of a conventional esteriflcationreaction. For instance, in referring to the analysis of the blowncastoroil above, it will be seen that such product contains acidity equivalentto 510% of the 'total saponifiable value. Such acidity can be removed byesterification with an alcohol such as methyl alcohol, ethyl alcohol,propyl alcohol, etc. On the other hand, insofar that glycerine is thenaturally-occurring alcohol present in most oils and fats, and alsoinsofar that glycerine is non-volatile, it is our preference to addsufilcient glycerine to such blown oil and keepit agitated at atemperature of approximately 125-170 C. until carboxylic aciditydisappears.

The blown oils, in their various forms, that is, in the ester form, saltform, or acid form, act similarly to fatty acids and their compounds.The typical reactions of fatty acids and amines, particularly primary orsecondary amines, may be indicated by the following:

(A) Salt formation R.COOH+R'NHH [HHR'N.H]OOC.R

(B) Amide formation R.COOH+HR'NH RCONR'H oils contain aldehydic acids.To the extent that aldehydic acids are present, certain amines,particularly primary or secondary amines, can enter into reactions whichare characteristic of the aldehyde radical and would have no connectionwhatsoever with blown oils which do not contain aldehydic acids. It isto be noted that as far as we are aware, the blown oils which we haveemployed in the manufacture of the preferred intermediate raw materialintended for polybasic car-boxy esterification, are free from anyaldehydic acids, and even if aldehydic acids are present, a complexamine of the kind herein contemplated would not be formed by virtueofreaction with the aldehydic group alone. As to reactions of the typeinvolved in the ammonolysis of aldehydlc acids, reference is made to U.S. Patent No. 2,079,764, dated May 11, 1937, to De Groote and Keiser.

(E) Still another type of reaction involves fatty acids and a tertiaryalkylolamine, or its functional equivalent, such as a tertiarybydroxyalicyclic amine. Such reaction may be indicated the followingmanner:

ncoon+oncini acoomn.

OHCzHa-N OH.CaH4-N +1110 OHCzHl OH-CJh However, it is to be noted thatif a blown oil is subjected to hydrolytic reaction so as to liberate thefatty acids or acid material present, the resultant materials areestolides, rather than the unaltered fatty acids. This has been pointedout in the De Groote, Keiser and Wirtel patent, to which previousreference has been made.

It is manifest that an eifort to react liberated blown oil fatty acidswith triethanolamine, for example, as indicated above, would not resultin derivatives of the fatty acids as they occur in the blown oil, butrather at the best, it would result in derivatives of the estolides. Forthis reason, materials of the kind employed as the intermediate rawmaterial intended for polybasic carboxy esterification cannot beobtained from liberated blown oil fatty acids, but must be obtained fromthe blown oils themselves. This is comparable to the situation indicatedin our co-pending application Serial No. 180,992, filed December 21,1937, in which it is shown that certain amines of a comparable type can.be derived from triricinolein, diricinolein, monoricinolein, ethylricinoleate, and the like, but cannot be derived from ricinoleic acid,because polyricinoleic acid would be formed.

If various oils or fats, and especially blown oils, are reacted in esterform with hydroxy tertiary amines, one obtains materials of the kindchar acterized by the fact that the fatty acid radicals derived from theblown oil are present'in the amine compound in an esterified form. Suchform is substantially unaltered, as compared with the original form aspresent in the blown oil itself. It may be well to point out two factsin regard to use of the blown oils and the fatty acids derivedtherefrom. We have previously pointed out that ordinary blown oils showsome acidity, and that our present reaction is concerned between hydroxytertiary amines and esters, and not fatty acids. However, since manyconventional blown oils contain as little as 5% free acidity, calculatedin the usual manner, it is obvious that this small acidity may beignored, and that for practical purposes the preliminary step intendedto insure complete esterification may be eliminated.

Secondly, we have referred to the acids present in blown oil as fattyacids. This is purely a matter of convenience. The expression fattyacids as usually employed, is intended to include unsaturated fattyacids of the kind which occur in natural oils and fats in the form ofesters, such as the glycerides. These fatty acids are sometimes referredto as higher fatty acids, and occur in oils such as olive oil,cottonseed oil, soy bean oil, corn oil, castor oil, neats-foot oil, andin marine oils such as menhaden oil, herring oil, sardine oil, pilchardoil, etc.

In some instances, these oils or the corresponding fatty acids, may beheated or oxidized so as to produce lower homologues or higher polymericforms. For instance, ricinoleic acid can be heated in such a manner asto produce hendecenoic acid, 011112202, which is a lower homologue ofoleic acid. Such materials are not fatty acids in the usual sense, sincethey do not occur as such in natural oils and fats, but they are hereinconsidered as fatty acids, since they represent lower homologues orisologues, and have the characteristic properties of the common fattyacids. They occur in blown oils, obtained by well-known procedure. Forinstance, when castor oil is heated and oxidized so as to produce blownor oxidized 011, one may at least partially break down the moleculehaving 18 carbon atoms into two molecules having, for example, 7 carbonatoms and 11 carbon atoms. Such acids of lower molecular weight maycombine in various manners to produce acids of higher molecular weightthan naturally-occurring fatty acids. Hence, the expression "fattyacids" is herein employed to refer not only to naturally-occurring fattyacids of the kind previously described, but also those kindred productsof higher or lower molecular weight, which appear cogenerically inconventional blown oils in the form of free acids or esters.

As to the production of the complex amines employed as intermediate rawmaterials intended for polybasic carboxy esterification in the presentinvention, attention is directed to our copending application Serial No.180,993, flied December 21, 1937. In view of the somewhat complicatedchemical nature of the intermediate raw materials intended for polybasiccarboxy esterincation, it may be well to point out the general type ofreaction involved in their manufacture. For convenience, the fatty acidsof blown oils will be considered as R..COOH, 'and the blown oil itselfwill be considered as the glyceride of these materials and indicatedthus: (R.C0O) CsHs.

Purely as a matter of simplicity,triethanolaminewillbeselectedasthetertiaryhydroxyamine for reaction witha selected blown oil. The reactions taking place in v ryins molecularproportions may be indicated in the following manner:

180' 0., for a suitable period of time, such as 2 to 8 hours. Mildagitation is employed. A catalyst such as sodium oleate, sodiumcarbonate, caustic soda. etc., may be present in amounts of aboutone-half of one percent or less. It is to be noted that the blown oilsare always in ester form and are not in acid form, thus are not subjectto decomposition of the kind which occurs when one attempts to directlyreact a blown oil fatty acid with a tertiary alkylolamine. It isfurthermore to be noted that this reaction does not take place to anyappreciable extent, if the blown oil has been converted into a soap orsalt. It is obvious that the blown oil fatty acids must be in the formof an ester, preferably a glyceryl ester, although some other esterifiedform, for instance, a derivative of a monohydric or dihydric alcohol,could be employed.

Four additional facts must be borne in mind in regard to thesecompounds, 1. e., the complex amines which are subsequently subjected topolybasic carbcxy esteriflcation. In the first place, these amines whichare employed as intermediate raw materials intended for polybasiccarboxy esterification in the present invention are not quaternaryammonium bases or salts thereof. The expression "quaternary ammonium" isproperly and conventionally applied to compounds'in which all fourhydrogen atoms of the ammonium radical NR4 have been replaced by ahydrocarbon radical, or oxy-hydrocarbon radical, as, for example, intrimethyl phenyl ammonium hydroxide.

Secondly, an important characteristic which must be recognized is thatthese amine compounds are not amides. It has been previously pointed outthat an amide formation involves a product in which there is' a directlinkage between the OILCaHA 0H.CsH|N 1 OHLCaHc 11.000 onclm 11.000.0m.(1 acoo-cm. onmm- 3 on.0.n.-N+0.n,(0m,

12.000 0110.11 0110.11. OILCsHI OILCJIc-N OILCsHa 11.000 omens-N 11.000011.0.11. n.coo.0,m (u) v OILCsHr-N sa.coo.cim n+2c,n, on

' 11.000 oncim 011.0111.

acoo-mm omcim 11.000 oacim-n n.000 01min. R.C00.CsH4

m R.C00--C$Hl OH.CsH|N R.000.0imrr+ 0.114011 11.000 011cm. R.000.0,m

The manufacture of these compounds is relatively simple. The selectedblown oil and the selected hydro!!! tertiary amine are mixed in suitableproportions and heated at some point above the boiling point of water,for instance, 110 0., and at a point below the decomposition point ofthe amine, or the blown oil, for instance,

carbozvlic carbon atom and the nitrogen atom in the amine. This is notthe case in the compounds employed as intermediate raw materialsintended for polybasic carboxy esterification in the present invention.

In the third place, it must be recognized that these compounds arederived only from basic tertiaryamines. The word ifbasic is employed toexclude amines having little or no basicity, such as the ordinaryaromatic amines, or any amine having at least one aryl radical directlyJoined to the amino nitrogen atom. For this reason, these amine productswhich are herein contemplated as demulsifying agents and whichnecessarily are characterized by freedom from any aryl groups as such,cannot be derived from aryl amines. They are derived solely from alkyl,alicyclic, or aralkyl amines having at least one hydroxyl group present.It is true that in the aralkyl amines there is an aryl group present.but it is not directly attached to the nitrogen atom, as in the case ofaryl amines, but in fact. represents nothing more or less than asubstituted alkylamine. For instance, we consider benzylamine as beingthe primary amine, phenmethyl amine.

Finally, it must be recognized that these ma terials have not lost anybasicity in the forms of the esterified amine and that they exhibit allthe properties of a basic amine, that is, they combine with water toform a base, presumably a substituted ammonium compound, but not aquaternary ammonium compound, insofar that there is always oneunsubstituted hydrogen atom of the ammonium radical present. Theycombine with various acids to form salts. For example, they may becombined with acetic acid, hydrochloric acid, lactic acid, chloraceticacid, nitric acid, butyric acid, phosphoric acid, oxalic acid, or anysuitable organic or inorganic acid, to form salts. It is understood thatthe reference in the specification and appended claims to the aminesincludes the basic form and the acid salts as well as the aminesthemselves. The characteristic properties of the final composition arecontributed, in part, by the amine, and it is immaterial whether it beconsidered as being in any one of the three following forms:

in which T represents the substituents of'the amino hydrogen radicals ofthe parent ammonia from which all amines are hypothetically derived, andX simply represents the acid radical of any acid employed.

In referring to the complex amines derived by reactions involving blownoils and triethanolamine, it is to be noted that the products may becharacterized by the following formula:

in which m is 1, 2 or 3, m is 0, 1 or 2, with the proviso that m+m=3,and n denotes any small whole number, preferably less than 10, and inthe case of triethanolamine, denotes t e number In the above formula andin all subsequent formulas, including such as appear in the appendedclaims, R.COO represents the blown oil fatty acid, which, as has beenpreviously explained, is in reality a collection or mixture of organicacids which appear cogenerically in the manufacture of blown oils.

If, instead of employing triethanolamine, ethyl diethanolamine or asimilar amine were employed, then the resulting products would beindicated by the following type formula:

in which m is 1 or 2. m is 0 or 1, m" is 1, with the proviso thatm+m'+m"=3; and n has the same significance as above.

In event that diethylaminoethanol were employed, it is manifest thatanother variation of the above formula would appear. It is also possibleto obtain compounds from such materials as acetylated triethanolamine,in which the acetyl radical has replaced one hydrogen atom of one of thehydroxy ethyl radicals. Acetic acid in this instance may be consideredtypical of the lower fatty acids which have less than 7 carbon atoms.

, If such monoacetylated triethanolamine were employed, the reactionproduct would be indicated inwhichmisl or2,m'is0orl,m"is1or2,

and n has the same significance as above.

m+m+m" must be equal to 3.

In the above formula RCO indicates an acyl radical derived from a lowmolecular weight fatty acid having less than 7 carbon atoms. Attentionis directed to the fact that the divalent aliphatic radical indicated byCnHin may be a radical such as a C2H4 radical, CaHs radical, 04H;radical, C5H1o radical, or it may be an alicyclic radical, or an aralkylradical, as will become obvious from the kind of amines subsequentlyenumerated. Furthermore, where the radical C1|H21l+1, which is a typicalalkyl radical, appears, it may be a methyl radical, ethyl radical,propyl radical, butyl radical, amyl radical, hexyl radical, octylradical, etc. On the other hand, instead of being a monovalent alkylradical, it may be a monovalent alicyclic radical, such as a cyclohexylradical, or it may be an aralkyl radical, such as a benzyl radical. Inthe claims appended hereto, it is understood that the expression alkylolincludes the hydroxy hydrocarbon radicals, whether derived from alkyl,alicyclic, or aralkyl radicals. It is furthermore understood in thehereto appended claims that the expression liydroxy alkyl includeshydroxy alicyclic, as well as hydroxy aralkyl radicals, provided that inthe latter the hydroxyl group is attached to the aliphatic side chain.Attention is also directed to the fact that the tertiary aminesinvolving the dihydroxy propyl radical C3H5(OH)2 may substitute for thehydroxy alkyl radicals of the kind described. It is also understood thatalkyl-oxy-alkyl radicals are the equivalent of an ordinary alkylradical, insofar that they might appear in products such as the.trihydroxy ethyl ether of triethanolamine, which may be indicated bythe following formula: N(C2H4OC2H4OH) 3. See other examples described inU. S. Patent No. 1,923,178, dated August 22, 1933, to Ulrich et a1.

Such material would be the obvious functional equivalent oftriethanolamine in reactions of the kind contemplated in the manufactureof the intermediate raw material intended for polybasic carboxyesteriflcation.

The amine employed as an intermediate raw material intended forpolybasic carboxy esteriflcation in the present invention might beindicated by the following formula:

in which m is 1, 2 or 3, m is 0, 1 or 2, with the proviso that m+m'=3; Tis an alkyl radical, or a radical of the type (R'COO.alkyl) or a hydroxyalkyl radical, and R'.COO represents an acid radical having less than 7carbon atoms. The expression alkyl" is used in the broad sensepreviously speciiled, and it is also to'be repeated that the amine maybe in the form of the base, or in the form of a salt.

Suitable bases which may be reacted with blown oils or completelyesteriiled blown oils, or esteriiled blown fatty acids to produce thereagents of the present invention. include: triethanolamine,diethanolalkylamines, such as diethanol ethylamine, diethanolpropylamine, etc.; tertiary glyceryl amines, such as monoglyceryldiethylamine, monoglyceryl dipropylamine, di-- glyceryl propylamihe,triglycerylamine, etc. Other examples include diethanol methylamine,tripropanolamine, dipropanol methylamine, cyclohexanol diethanolamine,dicyclohexanol ethanolamine, cyclohenl dicyclohexanol ethylamine, benzyldiethanolamine, dibenzyl ethanolamine, benzyl d-ipropanolamine,'tripentanolamine, trihexanolamine, ethyl hexyl 'ethanolamine, octadecyldiethanolamine, polyethanolamine, etc.

In indicating the various hydroxylated tertiary amines of the non-aryltype, which may be employed to produce the amine contemplated as theintermediate raw material intended for polybasic carboxy esteriilcationin the present'invention, it is desirable to indicate that amines of thetype where a hydroxy acyl radical replaces a hydrogen atom of thehydroxyl radical of the hydroxy tertiary amine, are not included withinthe broad class of hydroxy tertiary amines, unless there is anotherhydroxyl radical attached to the usual alkyl radical. For instance, ifdiethyl amino ethanol is treated with lactic acid so as to form lactylethanol diethylamine of the following formula:

cmcrLc-o-c r.

elm-N is substituted for triethanolamine in Example I. Complexamine-Example III Diamyl monoglyceroiamine (l-di-amyi amine propane2,8,diol) is substituted for triethanolamine in Example 1.

Complex mine-Example IV Dicyclohexylamine is reacted with glycerolmonochlorhydrin to give monoglyceryl dicyclohexylamine. This product issubstituted for triethanolamine in Example I.

Complex amine-Example V Dibenzylamine isreacted with glycerolmonochlorhydrin to produce monoglyceryl dibenzylamine. This product issubstituted for tri-' ethanolamine in Example 1.

Blown rapeseed oil of commerce, molecular weight figured as 990, issubstituted for blown castor oil employed in Examples I-VI, inclusive.

Complex amink-Example VIII Blown cottonseed oil, molecular weightfigured as 980, is substituted for blown castor oil in Examples I-VI,inclusive.

It is obvious that the amines of the kind above described will containhydroxyl groups attached to the fatty acid radical derived from blownoil, insofar that all blown oils show a'hydroxyl or then it isunderstood that such materials would -acetyl value. 8 previously hasbeendl not represent a hydroxy tertiary amine within the meaning orscope, as herein employed. 1!. on the other hand, triethanolamine weretreated with lactic acid so as to give monolactyl tri-J ethanolamine ofthe following composition:

on o

cnicmc-o-clm OHCsHI- one i then such compound would be included, due tothe presence of one or more hydroxyl radicals attached to the alkylradicals.

The following examples indicate various methods by which one can preparecomplex amines so of the kind which are suitable for polybasic carboxyesteriflcation:

Complex amine-Example I Blown castor oil of the kind previouslydescribed in detail is employed. For the sake of convenience, itsmolecular weight is considered as being 1000. Commercial triethanolamineand blown castor oil in the proportion of one mole of blown castor oilto three moles of triethanol- 7o amine are heated to a temperaturebetween 150 and 180 c. for about 2 hours. Mild agitation is employed.

Complex amine-Example II Triglycerylamine (tri:dihydroxy propylam'ine)out, such radicalsappear without change in the complex amine. It hasfurthermore been indicated that the complex amine may also have ahydroxyl radical as part of an alkylol radical. In

addition to this, there' may be foimd hydroxyl radicals present, due tocondensation with glycerol by means of an ether linkage. In any event,the complex amines oi the kind above described are reacted withpolybasic carboxy acids so as to produce an esteriilcation product, andpreferably, an esteriiication product of the kind in which there is atleast one residual carboxyl' xylene, and after the reaction is complete,the

naphthalic acid, oxalic acid, suberic acid, pimelic acid, .etc. Insubsequent examples, phthalic an-- hydride will be employed, because inmany instances it is most dairable to use the anhydride of an aromaticacid, and also because phthalic anhydride is obtainable at a relativelylow cost in a state of high technical purity. Furthermore, phthalicanhydride shows little or no tendency to produce objectionable secondaryreactions, and as a rule, one obtains almost theoretical yields of thedesired products. It is understood, however, that any polybasic carboxyacid may be employed, or any functional derivative thereof. It is alsoobvious that after reaction any free ionizable hydrogen atom can beneutralized in any suitable manner, for instance, by reaction withcaustic soda, caustic potash, ammonia, any basic amine or the like, orby further aterification with a mono-hydrlc alcohol, for example, suchas methyl alcohol or ethyl alcohol, or with a dihydric alcohol, such asethylene glycol, or a trihydric alcohol, such as glycerol. In view ofthis fact, the acid esters of carboxy acids, such as butyl hydrogenphthalate, propyl hydrogen phthalate, ethyl hydrogen oxalate, etc.,would be the functional equivalent of the polybasic carboxy acid itself.

Composition of matter-Example I Composition of matter-Example II Insteadof employing the complex amine of the kind previously described underthe heading "Complex amine-Example I, substitution of other complexamines of the kind indicated under Complex aminesExamples"II-VIII,inclusive, are employed.

Composition of mutton-Example III Examples of the kind preparedaccording to Composition of matter-Examples I and II, are modified bythe employment of maleic acid instead of phthalic acid.

Composition of matterE:z:umple IV In the example immediately preceding,oxalic acid is substituted for maleic acid with modification so that thereaction is conducted at a lower temperature to prevent decomposition ofthe oxalic acid-for instance, 110-120 C.

Composition of matterEmmple V Products of the kind described in theexample immediately preceding are prepared, but adipic acid issubstituted for oxalic acid.

We desire to emphasize that the products obtained in the above examplesmay be used in the form of the amine by direct contact with an emulsionwithoutmritact with water. They may be contacted with water, i. e., inthe form of a solution, so as to produce, in a greater or lesser degree,the amine base. Furthermore, any of the products above described may becombined with a suitable acid. Acetic acid may be employed. Hydrochloricacid is particularly desirable. In some instances acids, such as oleicacid or naphthenic acid, may be employed to give a suitable salt. Aspreviously pointed out, any carboxylic hydrogen atom may be replaced bya suitable metallic atom or an organic radical derived from an alcoholor from an amine. All such ionizable hydrogen atom equivalents areconsidered as the functional equivalent of the ionizable hydrogen atomsthemselves, and such neutralized forms are included in the scope of theappended claims as the equivalent of the acidic form. It is realizedthat where a free carboxyl and a basic amine residue exist in the samemolecule, there may be a tendency towards the formation of inner saltscomparable to sulfanilic acid; but due to the size of the moleculeinvolved and perhaps for reasons of steric hindrance, we are not awarethat such inner salts are formed.

In examining the method of manufacture of these complex amines, aspreviously illustrated, it is apparent that certain by-products appearas glycerine, monoor diglycerides, etc. From a practical standpoint itis unnecessary to separate these cogeneric materials, although it wouldbe possible to do so by conventional processes. It is quite possiblethat these materials which appear as part of the reaction masscontribute to a greater or lesser degree to the demulsifying power ofthe final material as obtained after polybasic carboxy esterification.It may be that some of these materials which appear in the reaction masscannot be completely identified as to their form. For instance, it is atonce possible to see that condensation products might be formed underproper conditions between complex amines of the kind employed and eitherglycerol or triethanolamine, by virtue of an ether linkage. Bothglycerol and triethanolamine may be present in the manufacture of someof the complex amines which are subsequently subjected to polybasiccarboxy esterification. In view of this fact, in the appended claims thecomposition of matter or product herein contemplated will be describednot only in terms of conventional chemical structure, but also in termsof the method of manufacture. The purpose of the claims which arecharacterized by reference to the method of manufacture is to includespecifically the general reaction mass produced in the manufacture ofthe amine bodies.

One should not lose sight of the fact, however, that the presentinvention is concerned particu-- larly with the employment of certainchemical compounds of definitely stated composition, which are presentin significant or predominant amounts in the mixtures obtained by thereactions described. Needless to say, the composition of matter is notlimited to any particular method of manufacture, except in the appendedclaims, in which specific reference is made to manufacturing procedure.

Briefly, then, the composition of matter herein contemplated depends ona reaction involving a polybasic carboxy acid or its functionalequivalent, as described, and the complex amine of the kind described,in such a manner as to involve boxy acid so as to form a salt in themanner indicated thus:

coon (R)=N+T/ [mun 00011200011 coon [RINK] O O C.T.C 0 ON.

Such reactions are purely salt formation. The materials of the kindherein contemplated, re-

gardless of their nature, are of the kindother than salt formation.

We desire to emphasize that the expression "polybasic carboxy acid, asit appears in the claims refers not only to the acid itself, but to anyfunctional equivalent; such as the anhydride, the acyl chloride, theacid salt, such as sodium hydrogen phthalate, amylamine hydrogenphthalate, ammonium hydrogen phthalate, benzyl amine hydrogen phthalate,cyclohexylamine hydrogen phthalate, ethanolamine hydrogen phthalate,diethanolamine hydrogen phthalate, triethanolamine hydrogen phthalate,orthe acid esters such as ethyl hydrogen phthalate, propyl 'hydrogenphthalate, butyl hydrogen phthalate, ethylene glycol hydrogen phthalate,dihydroxy propyl hydrogen phthalate, etc.

Attention is directed to the fact that the word Amidification has beenapplied to the reaction involving the replacement of an amino hydrogenatom by an acyl radical, without conventional limitation to a reactioninvolving ammonia. The

replacement of the amino hydrogen atom of a 7 primary amine or asecondary amine by an acyl radical has been considered as beingamidification, rather than the formation of a substituted amide or theformation of an imide or substituted imide. Such obvious departure fromconventional nomenclature has been for purposes of simplicity and toshow the similarity between certain reactions.

Conventional demulsifying agents employed in the treatment of oil-fieldemulsions are used as such, or after dilution with any suitable solvent,

such as water, petroleum hydrocarbons, such as gasoline, kerosehe, stoveoil, a coal tar product, such as benzene, toluene, xylene, tar,acid oil,cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols,such as methyl alcohol, ethyl alcohol, denatured alcohol, propylalcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may beemployed as diluents. Miscellaneous solvents, such as pine oil, carbontetrachloride, sulfur dioxide extract obtained in the refining ofpetroleum, etc., may be employed as diluents. Similarly, the material ormaterials herein described may be admixed with one or more of thesolvents customarily used in connection with conventional demulsifyingagents. Moreover, said material or materials may be used alone or inadmixture with other suitable well known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in awater-soluble form, or in an oil-soluble form, or in a form exhibitingboth oil and water solubility. Sometimes they may be used in a formwhich exhibits relatively limited water solubility and relativelylimited oil solubility. However, since such reagents are sometimes usedin a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000. such anapparent'insolubility in oil and water is not significant, because saidreagents undoubtedly have solubility within the concentration employed.This same fact is true in regard to the new demulsifying material orcomposition herein described.

mean? We desire to point out that the superiority of the reagent ordemulsifying agent constituting our present invention is based upon itsability to treat certain emulsions more advantageously and at a somewhatlower cost than is possible with other available demulsifiers, orconventional mixtures thereof. It is believed that the particulardemulsifying agent or treating agent herein described will findcomparatively limited application, so far as the majority of oil fieldemulsions are concerned; but we have found that such a demulsifyingagent has commercial value, as it will economically break or resolve oilfield emulsions in a number of cases which cannot be treated as easilyor at so low a cost with the demulsifying agenicheretofore availa e.

In using the herein described new demulsifying agent to resolve thepetroleum emulsion, the said demulsifying agent is brought into contactwith or caused to act in any of the various ways, or by any of thevarious apparatus now generally used to resolve or break petroleumemulsions with a chemical reagent, the above procedure being used eitheralone, or in combination with other demulsifying procedure, such as theelectrical dehydration process.

Having thus described our invention, what we claim asnew and desire tosecure by Letters Patent is:

1. A composition of matter, comprising the products derived byesterification reaction between (a) a polybasic carboxy acid, and (b)the hydroxylated product derived by an alcoholysis reaction, undersubstantially anhydrous conditions, between a blown oil and a tertiaryhydroxy amine having at least onehydroxyl group aliphatically bound tothe amino nitrogen atom and free from amino nitrogen linked arylradicals, within the molal ratio of 1:1 and 1:3 at a temperature abovethe boiling point of water and below the point of decomposition; saidlast -mentioned reaction being conducted in a mansame moleculecontaining the basic nitrogen atom.

2. A composition of matter, comprising the products derived byesterification reaction between (a) a polybasic carboxy acid, and(b) thehydroxylated product derived by anvalcoholysis reaction, undersubstantially anhydrous conditions, between a blown oil andtriethanolamine within the molal ratio of 1;1 and 1:3, at a temperatureabove the boiling point of water I and below the point of decomposition;said last mentioned reaction being conducted in a manner to yield asubstantial quantity of basic material in which the blown oil fattyacid'radical is attached to the basic nitrogen atom through a carbonatom chain by replacement of the hydrogen of at least one hydroxyl ofthe hydroxy amine by the acyl group of the blown oil fatty acid radical;said first mentioned esterification reaction involving a. polybasiccarboxy acid and being conducted in a manner so as to react 1s with atleast one hydroxyl radical of the blown oil fatty acid radical whichis'a part of the same molecule containing the basic nitrogen atom.

3. A composition of matter, comprising the products derived byesteriflcation reaction between (a) apolybasic carboxy acid, and (b) thehydroxylated product derived by an alcoholysis reaction, undersubstantially anhydrous conditions, between a blown castor oil andtriethanolamine within the molal ratio of 1:1 and 1:3, at a temperatureabove the boiling point of water and below the point of decomposition;said last mentioned reaction being conducted in a manner to yield asubstantial quantity of basic material in which the blown oil fatty acidradical is attached to the, basic nitrogen, atom through a carbon atomchainby replacement of the hydrogen of at least one hydroxyl of thehydroxy amine of the acyl group of the blown oil fatty acid radical;said first mentioned esterification reaction involving a polybasiccarboxy acid and being conducted in a manner so as to react with atleast one hydroxylg'adical of the blown oil fatty acid radical which isa part of the same molecule containing the basicnitrogen atom,

4. A composition of matter; comprising the product derived byesteriiication reactions between (a) a polybasic carboxy acid, and (b) achemical compound of the type indicated by the formula:

in which m is 1, 2,*or a, m is 0,1, or 2, with the product derived byesterification reactions bet'ween (a) a polybasic carboxy acid, and (b)a chemical compound of the type indicated by the formula:

, in which m is 1 or. 2, and m is 1 or 2, with the proviso that m+m'=3,T is a hydroxy alkyl radical, and R.COO is a blown oil fatty acid'radical;' said product being further characterized. by the fact thatthe esterification reaction with the aforementioned polybasic carboxyacid involves at least one hydroxyl radical of a blown oil fatty acidradical indicated by the symbol R.

6. A composition of matter, comprising the product derived byesterification reactions between (a) a polybasic carboxy acid, and (b) achemical compound of the type indicated by theinwhichmis1or2,andm'is1or2,withthe proviso that m+m'=3, T is av hydroxyethyl radical, and R.COO is a blown oil fattyacid radical; said productbeing further characterized by the fact that the esteriflcation reactionwith the aforementioned polybasic carboxy acid involves at least onehydroxyl radical of a blown oil'fatty acid radical indicated by thesymbol R.

7. A composition of\matter, comprising the product derived byesteriflcation reactions/between (a) a polybasic car-boxy acid, and (b)a chemical compound of the type indicated by the formula: I

' tw -em inwhichmis1or2,andm'islor2,withthe proviso that 'm+m'=3, T is ahydroxy ethyl radical, and R'.COO is 'a blown oil fatty acid radicalderived from castor oil; said product being further characterized by thefact that the esteriflcation reaction with the aforementioned polybasiccarbony acid involves at leastone hy-v droxyl radical of the blowncastor oil fatty acid radical indicated by the symbol R.

MELVIN DE GROOTE.

v M. m, Jl.

